Tobacco and tobacco substitute material including metal chelate compounds

ABSTRACT

In a smokable product comprising a cellulose-based combustible material, the improvement which comprises incorporating therein at least one chelate compound of the stoichiometric formula.

United States Patent [191 Eicher et a1.

[ TOBACCO AND TOBACCO SUBSTITUTE MATERIAL INCLUDING METAL CHELATECOMPOUNDS [75] inventors: Theo Eicher; Friedemann Miiller;

Klaus-Werner Krebs, all of Dormagen, Germany [73] Assignee: Haarmann &Reimer GmbH,

Holzminden, Germany 22 Filed: Nov. 15, 1972 21 Appl. No.: 306,655

[44] Published under the Trial Voluntary Protest Program on January 28,1975 as document no.

[30] Foreign Application Priority Data Nov. 19, 1971 Germany 2157370Mar. 29, 1972 Germany 2215412 [52] US. Cl 131/2; 131/262 A; 131/17 R[51] Int. 1C1. A24B 15/00; A24B 15/02 [58] Field of Search 131/2, l5,17, 200, 201, 131/10-10.9, 140-144, 261, 262, 264, 265, 266, 267

[56] References Cited UNITED STATES PATENTS 2,108,860 2/1938 Kauffman131/265 X 2,171,986 9/1939 Poetschke 131/15 R 3,109,436 11/1963 Bavleyet a1. 131/262 A 3,459,195 8/1969 Silberman 131/2 X 3,461,879 8/1969Kirkland 131/2 3,529,602 9/1970 Hind et a1. 131/2 3,572,348 3/1971Norman et a1 131/262 A 3,724,469 4/1973 Reynolds et a1. 131/266 X OTHERPUBLICATIONS The Chemistry and Technology of Tobacco (Text), by

[ Dec. 9, 1975 A. A. Shmuk, published by Pishchepromizat, Moscow, 1953and by the The National Science Foundation, 1961, pp. 588, 590, 602 and603 cited.

Dangerous Properties of Industrial Materials, (Text) by N. Irving Sax,p. 888 cited pub. by the Reinhold Book Corp., N.Y. (1968).

Primary Examiner-Melvin D. Rein Attorney, Agent, or FirmBurgess,Dinklage &

Sprung [57] ABSTRACT In a smokable product comprising a cellulose-basedcombustible material, the improvement which comprises incorporatingtherein at least one chelate compound of the stoichiometric formula.

K [Me,,R,,],,.

in which K is an alkaline earth metal or divalent manganese, Me istrivalent iron or aluminum, R is the radical of a chelate-formingorganic carboxylic acid, and w, x, y, and z are integers up to about 5,

the chelate compound being incorporated in an amount ranging from about0.5 to 70% by weight of the combustible material. Preferably R is theradical of an organic dicarboxylic acid containing 2 to 8 carbon atomsor a hydroxyor keto-substituted carboxylic acid. The product may alsocontain fillers, compounds which split off ammonia, oxidizing agents,ammonium salts of polymeric acids, low sulfur-content proteins and/ortobacco extracts. The product may be used as such or in blends withtobacco as cigarettes, cigars or pipe tobacco.

22 Claims, No Drawings TOBACCO AND TOBACCO SUBSTITUTE MATERIAL INCLUDINGMETAL CHELATE COMPOUNDS This invention relates to smoking products whichcontain combustible materials based on cellulose together with otherconstituents, in particular metal chelates, and to a process forproducing them.

It is known how to produce a smokable material, which is not naturaltobacco, from tobacco waste products or mixtures thereof with otherplant materials, as well as from natural or synthetic non-tobaccoproducts, which are made up into paper-like webs or foils or fibres.According to DOS No. 1,900,491, for example, smoking materials can beproduced from cellulose, cellulose derivatives or starch using certaininorganic fillers which keep the material glowing. According to US. Pat.No. 3,461,879, hydrated magnesium citrate and calcium tartrate may beadded to certain cellulose derivatives to assist the combustion process.

The non-tobacco smokable products produced by the previously knownprocesses do not have satisfactory organoleptic properties but on thecontrary organoleptic properties which are unpleasant to a greater orlesser degree, e.g. sharpness and poor aroma in the main and sidestreams. For example, even tobacco substitute products with only a lowsulphur content, e.g. in the form of sulfates, are found to produce asmoke with an unpleasant sulfidic flavor. Tobacco substitute productswith a high cellulose content which contain the alkali metal, alkalineearth metal and iron salts normally present in smokable products giverise, when allowed to glow, to a sharp and biting smoke with acellulosic flavor and leave behind a persisting astringent effect in themouth. Moreover, the known nontobacco smoking products generallymanifest an organoleptic incompatibility with numerous sorts of tobaccowhen blended with them.

For example, the addition of substances such as magnesium citrate orcalcium tartrate which, according to the prior art, may be added to asmoking material to improve its glowing properties, results in smokingproducts which are completely unsatisfactory in their organolepticproperties. The sharpness of the smoking products is not sufficientlyreduced. A particularly disturbing feature of such a product is that theburning of the cellulosic material in it gives rise to an unpleasantflavor (cellulosic flavor) and to a smellof burnt paper, which arepractically the same as the smell and flavor of burning pure cellulose.These products are therefore not economically utilizable as smokableproducts or as additions to smokable products.

Other disadvantages of the known non-tobacco smokable products are theirlow bulk volume, their generally insufficient wet strength and their lowmechanical strength, which leads to an excessive production of dust inprocessing.

It is accordingly an object of the present invention to provide asmokable product which has desirable organoleptic properties and arelatively low content of undesired condensible materials in its smokeand which is free of the disadvantages noted hereinabove.

These and other objects and advantages are realized in accordance withthe present invention pursuant to which there is provided acellulose-based combustible material having incorporated thereintrivalent metal chelate compounds of alkaline earth metals and/or ofmanganese, the trivalent metal chelate compounds being complex anionswhich contain trivalent iron or aluminum as the central atom and theanions of chelate-forming organic carboxylic acids as ligands.

A smokable product comprising a combustible material based on cellulosehas now been found characterised in that the smokable product containsmetal (111) chelate of alkaline earth metals and/or of manganese (II),the metal (111) chelate compounds being complex anions which containtrivalent iron or aluminium as the central atom and the anions ofchelate-forming organic carboxylic acids as ligands.

The alkaline earth metal-metal (I1I)-chelate compounds used in theproducts according to the invention may be, for example, the calcium ormagnesium compounds.

The chelate compounds used in the products according to the inventionwill hereinafter be referred to simply as chelates.

The term chelate is therefore used to denote complex salts with achelate structure which contain alkaline earth metal ions or manganese(11) ions as the cation, and as the anion, a chelate-complex consistingof iron (III) ions or aluminium ions as the central atom andchelate-forming organic carboxylic acids as ligands (see, e.g., A. E.Martell, M. Calvin, Die Chemie der Metall-Chelat-Verbindungen, page 204,Verlag Chemie, Weinheim (1958)).

Smokable products according to the invention may preferably contain atleast one chelate compound of the stoichiometric formula I [Mer 1..

in which:

K is an alkaline earth metal or divalent manganese,

Me is trivalent iron or aluminum,

R is the radical of a chelate-forming organic carboxylic acid, and

w, x, y and z are integers up to about 5,

In general, x denotes l or 2 and y denotes integers of from 1 to 4, andz resp. w denote the number of divalent cations K resp. anions anddepend on the number of free negative valencies'remaining in the anioncomplex.

The cations of the chelates contained in the products according to theinvention may be calcium, magnesium or manganese (11), preferablymagnesium or manganese (11).

In some cases, it has been found advantageous partly to replace thecations of the chelates by hydrogen so that the corresponding acid saltsare formed. Acid chelates which contain one hydrogen ion are preferred.

Chelate-forming organic carboxylic acids, hereinafter referred to asChelate formers" (see A. E. Martell, M. Calvin, Die Chemie derMetallchelatverbindungen (pages 462-517) Verlag Chemie, Weinheim (1958),are, for example, organic carboxylic acids which contain 2 to 8 carbonatoms and in addition to the carboxylic group contain at least onehydroxyl group, keto group or additional carboxyl group.

Chelate formers may therefore for example be dicarboxylic acids. Thefollowing are mentioned as examples of dicarboxylic acids: oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid,fumaric acid and itaconic acid. Particularly preferred dicarboxylicacids are oxalic acid, malonic acid and succinic acid. Hydroxy acidssuch as hydroxymonocarboxylic acids, hydroxydicarboxylic acids andhydroxytricarboxylic acids may also be chelate formers. Examples of suchhydroxymonocarboxylie acids are: lactic acid, glycolic acid,B-hydroxypropionic acid, glyceric acid and hydroxypivalic acid. Glycolicacid and glyceric acid are particularly preferred hydroxymonoearboxylicacids. The following are mentioned as examples of hydroxydicarboxylicacids and hydroxytricarboxylic acids: hydroxymalonic acid, malic acid,tartaric acid, 2-hydroxglutaric acid, 3-hydroxyglutaric acid,3-methylmalic acid, 2,5-dihydroxyadipic acid, 2,4-dihydroxyadipic acidand citric acid, among which malic acid, tartaric acid and citric acidare preferred Monoand dicarboxylic acids derived from pentoses andhexoses, for example, may also be chelate formers. Examples of thesechelate formers are the isomeric monocarboxylic acids known as uronicacids, for example, glucuronic acid, galacturonic acid and mannuronicacid, the compounds known as saccharic acids, e.g. saccharic aciditself, manosaccharic acid and idosaccharic acid, as well as theisomeric mucic acids (galactaric acids). The pentaric acids derived frompentoses, ribotrihydroxyglutaric acid and xylotrihydroxyglutaric acidmay also be mentioned as examples. Ketocarboxylic acids containing 3 to8 carbon atoms may be used as chelate formers which contain a ketogroup. Examples of keto carboxylic acids are: pyroracemic acid,acetoacetic acid. laevulinic acid and mesoxa lic acid.

The preferred chelate formers used are diearboxylic acids andhydroxycarboxylic acids, in particular oxalic acid, glyceric acid,glycolic acid, malic acid, tartaric acid, galactaric acid, saccharicacid and citric acid.

it has been found particularly advantageous, for example, to usechelates of the general formula (I) which have the followingcomposition: magnesium-iron(lll)- glycolate,magnesium-iron-(lll)-oxalate, magnesiumiron-(III)-citrate,magnesium-iron-Ill)-tartrate, magnesium-iron-(lll)-galactarate,magnesiumiron-(lll)' saccharate, magnesium-aluminum glycolate,magnesiumaluminum oxalate, magnesium-aluminum citrate, magnesiumaluminumtartrate, magnesium-aluminum galactarate, magnesium-aluminum saccharate,man ganese-iron-(III)-glycolate, manganese-iron-(Ill)-oxalate,manganese-iron-(llI)-citrate, manganese-iron- (lll)-tartrate,manganese-iron-(lll)-galactarate, manganese-iron-([ID-saccharate,manganese-aluminum glycolate, manganesealuminum oxalate,manganesealuminum citrate, manganese-aluminum tartrate,manganese-aluminum galactarate, manganese-aluminum saccharate.

The chelates used in the smokable products according to the inventionmay, for example, have the composition indicated in Table (l). Thecompounds shown in Table (1) correspond to the general formula (1)(K,[Me, R,,],,.), in which K represents magnesium, calcium or manganese(11), Me represents iron (111) or aluminum and R represents thechelate-forming carboxylic acid. The values indicated for x, y, w and zare substituted in the general formula (1) in each case to give thesummation formula of the given example of chelate.

. Table l-continued R X y free negative 7. w

valences citrate l 3 6 3 l citrate 2 3 6 3 l tartrate l l l l 2 tartratel 2 3 3 2 tartrate l 3 3 3 2 tartrate 2 3 4 2 l oxalate 1 2 l l 2oxalate l 3 3 3 2 oxalate l 4 4 2 l glycolate l 2 1 l 2 glycolate l 3 33 '2 galactarate l l l l 2 galactarate 1 l 2 l 1 galactarate l 2 3 3 2galactarate l 3 3 3 2 Particularly preferred chelate formers aretartaric acid, citric acid and galactaric acid.

Particularly preferred chelates are magnesium-iron- ([ll)-tartrate,magnesium-iron-(lll) citrate, magnesium-aluminium tartrate,magnesium-aluminum citrate, manganese-iron-(IlI)-galactarate andmanganese-iron- (IIl)-citrate.

The chelates contained in the smokable products according to theinvention may be prepared in known manner in aqueous solution, e.g. byreacting the iron or aluminum salts of the desired chelate-formingcarboxylic acids with calcium magnesium or manganese salts, which may beadded as hydroxides, carbonates or salts of the correspondingchelate-forming carboxylic acids (see DRP 514,504; Hanus and Quadrate ZAnorg. Chem. 63, page 314 (1909) and W. Franke, Liebig Ann. Chem. 486,page 248 (1931)).

Examples of combustible materials based on cellulose are:cellulose-containing plant materials, particularly tobacco, tobaccowaste products, e.g. stalks, ribs or fragments, decomposedcellulose-containing plant material such as for example hay, straw,lupins or fern, as well as cellulose or wood pulp or cellulosederivatives, alone or as mixtures. The cellulose derivatives used maybe. for example, carboxymethyl cellulose, hydroxyethylcellulose ormethyl cellulose.

The combustible materials used may also be polymerlike lower molecularweight fragments of cellulose obtained by thermal degradation ofcellulose, or they may be cellulose derivatives prepared by chemicalprocesses, particularly by alkaline or acid oxidation.

Particularly satisfactory results are obtained by the use of tobacco orof paper-like webs composed of tobacco waste products or of cellulose orwood pulp.

The smolaable products according to the invention generally containabout 0.5 to by weight of chelate, based on the total weight ofcombustible material used in the products. It has been foundadvantageous to adjust the quantity of chelate according to thecellulose content of the combustible material used. lf, for example, thecellulose content ofthe combustible material is about 10% by weight,then the quantity of chelate used is preferably about 1 to 15% byweight, based on the total weight, and in particular about 5 to 10% byweight. If the cellulose content of the combustible material is higherthan 70% by weight, the quantity of chelate used, based on the totalweight, is about 10 to 70% by-weight, preferably 25 to 50% by weight.

According to a preferred embodiment of the invention, the smokableproducts contain a filler. By fillers are meant minerals, inorganicsalts and oxides which have no effect on the flavor under smokingconditions, for example silica, silicates, mica, alumina, dolomite,magnesite and chalk or carbonates, phosphates and oxides of aluminumiron, magnesium and calcium. Inert fillers which split off water undersmoking conditions may also be used. This elimination of water may bedue to the presence of a large quantity of water of crystallization inthe filler or it may be due to chemical decomposition, e.g. from metalhydroxides. Fillers which have been found to be particularlyadvantageous are the hydroxides and hydrated oxides of aluminum andiron, natural silicates such as vermiculite and kaolin, precipitatedsilicates such as silicic acid, silica gel, silica sol and alkalineearth metal and alkali metal silicates, the hydrated oxides of aluminumand/or silicic acid being preferred. It is generally suitable to useabout 1 to 70% by weight of fillers, based on the total quantity ofsmokable product. The quantity used is preferably about to 50% byweight.

It has been found particularly advantageous to use the fillers in ratioswithin the range of about 9:1 to 1:9, inclusive, based on the quantityof chelate used.

According to another preferred embodiment of this invention, thesmokable products contain compounds which split off ammonia undersmoking conditions, in particular,-ammonium salts of inorganic acids andorganic carboxylic acids, salts of amino acids and acid amides.

The preferred compounds which split off ammonia under smoking conditionsare the acid and neutral ammonium salts of inorganic acids such ascarbonic acid, nitric acid and phosphoric acid, particularly theammonium salts of phosphoric acid.

Good results are also obtained with the acid and neutral ammonium saltsof organic carboxylic acids which have a carbon to oxygen ratio in theoverall formula within the range of about 2:1 to 1:2, inclusive,preferably about 1:1 to 1:2, inclusive. Suitable ammo nium salts aretherefore, for example the ammonium of monocarboxylic acids such asformic acid and acetic acid, ammonium salts of dicarboxylic acids suchas oxalic acid, malonic acid and succinic acid, ammonium salts ofhydroxymono-, hydroxydiand hydroxytricarboxylic acids such as glycolicacid, lactic acid, B- hydroxypropionic acid, glyceric acid, malic acid,tartaric acid and citric acid, and the ammonium salts of monoanddi-carboxylic acids derived from pentoses and hexoses, such asglucuronic acid, galacturonic acid and mannuronic acid, saccharic acidand the isomeric mucic acids. Ammonium tartrate and ammonium citrate arepreferred.

The ammonium salts corresponding to the chelates according to theinvention (1(" representing ammonium in the general formula (I) are alsovery advantageous to use as compounds which split off ammonia. Thefollowing ammonium chelate compounds are preferably used:ammonium-iron-(IlI)-glycolate, ammonium-iron-(llI)-oxalate,ammonium-iron-(I1I)-citrate, ammonium-iron-(lII)-tartrate, ammonium-iron(III)- galactarate and ammonium-iron-(IIl)-saccharate as well asammonium-aluminum glycolate, ammoniumaluminum oxalate, ammonium-aluminumcitrate, ammonium-aluminum tartrate, ammonium-aluminum galactarate andammonium-aluminum saccharate.

Ammonium-iron-(III)-citrate, ammonium-iron-(Ill)- tartrate,ammonium-iron-(lII)-galactarate, ammoniumaluminium citrate andammonium-aluminum tartrate are particularly preferred.

It has also been found advantageous to use acid amides as compoundswhich split off ammonia, for example acetamide, propionamide, succinicacid monoamide and diamide and particularly urea. Ammonium, magnesium ormanganese (II) salts of aminoacids may also be used as compounds whichsplit off ammonia, the aminoacids being preferably glycine, serine,lysine, arginine, leucine, proline, valine, aspartic acid or glutamicacid. Magnesium glutamate and manganese glutamate are particularlypreferred as compounds which split off ammonia.

The compounds which split off ammonia are used, for example, inquantities of about 1 to 25% by weight, based on the smokable product,preferably about 5 to 15% by weight.

It has been found suitable to adjust the quantity of compounds whichsplit off ammonia under smoking conditions so that the acids which areformed in the smoke when the smokable product smolders are neutralized.This can easily be controlled by pH measurements in the main streamsmoke. The compounds which split off ammonia are advantageously added insuch quantities that the pH of the main stream smoke is adjusted toabout 5 to 8, preferably 6 to 7.5.

According to another special embodiment of the invention, the smokableproducts contain about 0.01 to 7% by weight, preferably about 1 to 5% byweight based on the total weight of the smoking product, of an oxidizingagent. By oxidizing agent is meant a substance which improves theglowing of the smoking product.

The oxidizing agents used may be, for example, salts of nitric acid,particularly alkali metal or alkaline earth metal nitrates. The nitratespreferably used are potassium nitrate and/or sodium nitrate.

Oxidizing agents which have been found to be particularly advantageousin the smokable products according to the invention are compounds ofmanganese (VII), in particular alkali metal permanganates, e.g.potassium permanganate.

According to another preferred embodiment of the invention, the smokableproducts contain about 0.01 to 10% by weight, preferably about 0.1 to 5%by weight, based on the smokable product, of ammonium salts ofpolygalacturonic acids such as pectin, alginic acid or gum arabic and/orammonium salts of carboxymethyl cellulose.

Satisfactory organoleptic properties are also obtained when using about0.01 to 5% by weight, preferably about 0.1 to 3% by weight, based on thesmokable product, of proteins which have a low sulfur content, e.g.zein, hordein or gliadin, as well as the alcoholic extracts of theseproteins, e.g. the ethanol extracts. Apart from liberating ammonia inthe smokable products, these compounds impart a pleasant plant flavorwith a tobacco-like note. The smokable products obtained by this methodare completely compatible in their aroma with any tobacco with whichthey may be blended.

According to another preferred embodiment, the smokable products containabout 0.1 to 50% by weight, based on the total weight of smokableproduct, of tobacco constituents. Tobacco constituents are substances orgroups of substances which can be obtained from tobacco by knownprocesses, e.g. by pressing, distillation or extraction. It is preferredto use tobacco constituents which have been obtained by extractioncarried out, for example, with water or organic solvents.

The combustible material which forms the basis of the smokable productsaccording to the invention may be in the form of a paper-like-web, afleece, a foil or a thread or strand, cut or uncut. Th e'paper-likewebs, fleeces or the like may be produced by known technical processes(see Ullmanns Enzyklopadie der techn. Chemie, 3rd Edition, Volume 13,pages 122-130 (1962) and ibid. Volume 17, pages 288 to 296 (1966)).

It has been found particularly advantageous to produce the productaccording to the invention in the form of paper-like webs with a surfaceweight of about 10 to 250g/m preferably about to 60 g/m and thicknessesgenerally in the region of about 10 to 120 preferably about to 60 u, andparticularly about to 45 1,. i

The smokable products according to the invention may be produced, forexample, by applying the chelates used according to the invention in theform of a solution, preferably an aqueous solution, to the combustiblematerial based on cellulose which is in the form of a paper-like web, afleece, a foil or a thread or strand, cut or uncut. Application of thechelate solution may be carried out, for example, by immersing thecombustible material in a bath of the solution of chelate compounds andthen drying it, advantageously at temperatures of about 50 to 120C.Alternatively, the material may be sprayed or painted with the solutionof chelates. Furthermore, the chelates may be introduced directly intothe starting mixture from which the combustible material is produced,e.g. in the form of paperlike webs, fleeces, foils, threads or strands.

The chelates may, for example, be introduced directly into a castingsolution containing the combustible material. These casting solutionsmay advantageously contain about 0.1 to 20% by weight of a binder, inaddition to optional fillers compounds which split off ammonia,oxidizing agents and tobacco constituents. The binders may be forexample polysaccharides or their derivatives, gum arabic, starch,carboxymethylcellulose with a low alkaline content and/orammonium-carboxymethylcellulose. If the binder comprises a combustiblematerial based on cellulose, it may, of course, take over the functionof combustible material in the products according to the invention. Theproducts according to the invention may be produced, for example, bypouring the casting solution on to an endless band and by drying at 50Cto 120C.

The smokable products according to the invention are preferably producedusing paper-like webs or fleeces.

The amount of chelates taken up by the foil or fleece may be controllednot only by the various operating conditions but also by the structureof the foil and the viscosity and concentration of the chelate solution.Adjustment of the viscosity can be achieved for example by varying theconcentration of the solution of chelates or by adding thickeners suchas a carboxymethylcellulose which has a low alkaline content, ahydroxyethyl, cellulose, pectins, gum arabic, alginates, galactomanan,starch and derivatives thereof. A high uptake of salts into the smokableproduct is possible, for example, by using concentrated, highly viscoussolutions.

The fillers which may be used according to a preferred embodiment of theinvention may be incorporated into the combustible material at the sametime as the chelates. Alternatively, they may be incorporated partly orcompletely in a separate stage of the process before or after thetreatment with chelates. Incorporation of the fillers may be carried outby known technical methods employed for producing paper-like webs,fleeces or foils which contain fillers.

The compounds which split off ammonia, which may also be used accordingto a preferred embodiment of the invention, may be introduced into thecombustible material either together with the chelates or in a separatestage of the process before or after incorporation of the chelates.Introduction of the compounds which split off ammonia is carried oute.g. by spraying or painting the combustible material with aqueoussolutions of the compounds which split off ammonia, or by immersing thematerial in such solutions, and then drying the material.

The oxidizing agents used according to a preferred embodiment of theinvention may be introduced into the combustible material at the sametime as the chelates or before or after their incorporation into thematerial.

Introduction of the oxidizing agents is carried out e.g. byspraying orpainting the combustible material with an aqueous, alcoholic or acetonicsolution of the oxidizing agent or by immersing the material in such asolution.

The ammonium salts of polygalacturonic acids used according to anotherpreferred embodiment of the invention, as well as the proteins with alow sulfur content and their alcoholic extracts, and the tobaccoconstituents which are used according to a further embodiment of theinvention, may be introduced together with the chelates or before orafter the latter are incorporated into the combustible material. Theyare preferably incorporated into the combustible material together withor after the chelates.

In all the embodiments, the usual additives employed in tobaccoprocessing, e.g. moisturizing agents, flavor and nicotine, may beintroduced in the same or separate process steps.

The preferred embodiments of the process for producing the smokableproducts according to the invention may, of course, be applied in anycombination.

When the products according to the invention are compared with smokableproducts produced from the same combustible material to which thecombustion modifying substances of the prior art have been added, it isfound that when smoked, the products of the invention areorganoleptically less acrid. they have a pleasant, mild flavor withoutany astringent effect the aroma is improved. For example, when thesmokable products according to the invention are added to tobaccos whichhave a cellulosic sharpness or when such tobaccos are treated by theprocess according to the invention, then not only is the sharpnessreduced but the aroma of these tobaccos is greatly enhanced. Thesmokable products according to the invention are not only distinguishedby their exceptionally low condensate value but also have excellentglowing properties. The smokable products according to the invention areparticularly distinctive in producing a smoke which has no celluloseflavor and therefore no organoleptically irritating components.

Smoke analyses of smokable products according to the invention show inpart a considerable reduction in physiologically harmful substances ascompared with those found in tobacco. Thus, a cigarette containing theproducts according to the invention is found to have a substantiallylower phenol content and hydrocyanic acid content as well assubstantially lower condensate values than a cigarette comprisingtobacco. For

example, when comparing cigarettes produced from cellulose foilscontaining a filler and treated with chelates with cigarettes producedfrom tobacco, the phenol content in each cigarette was found to bereduced by more than 90%, the hydrocyanic acid content by about 40% andbenzpyrene content by about 25%. The quantity of dry condensate could bereduced by about 80 to 90% compared with that in tobacco.

The addition of the smokable products according to the invention totobacco can have an advantageous influence on the burning properties oftobacco, especially in that the amount of physiologicallyharmfulsubstances in the smoke is substantially reduced, as was to be expectedfrom the individual components of these mixtures.

The aroma and flavor of the smokable products can be varied and ifdesired, for example, the flavor can be neutralized, by varying thechelates used as well as the other components which are added accordingto various preferred embodiments of the invention, e.g. by adjusting theratios of the quantity of chelate compounds to the quantity of compoundswhich split off ammonia under smoking conditions. By means of theprocess according to the invention therefore, the char acteristics ofthe smokable productscan easily be adjusted to those of varioussynthetic aromatic components or aromatic components obtained byextraction from tobacco as well as to those of various kinds of tobaccosuch as Burley, Virginia or Oriental with which the smokable productsmay be blended. A harmonious blend of tobacco aromas and flavors cantherefore be obtained in every case and constantly reproduced.Application of the chelates contained in the products according to theinvention is found to be particularly advantageous because thesecompounds are generally readily soluble in water. Homogeneousdistribution of the chelates in the smokable products can thereforeeasily be achieved in one step. Due to their low tendency tocrystallization and their hygroscopic properties, the products obtainedby the process according to the invention are smooth and elastic andtherefore particularly easy to work with.

They have a tobacco-like texture and in their processing properties,such as the ease with which they can be cut and mixed, they arecomparable with natural tobacco. The bulk volume can be increased to avalue higher than that of an equal quantity of tobacco by adjusting thesurface weight of the support, for example to a value of about l to 60g/m so that, by blending tobacco with such smokable products, theindividual smokable article, such as a cigarette, cigar or pipeful oftobacco, is reduced in weight, and consequently the total quantity ofsubstance smoked, and hence the quantity of condensate produced, isstill'further reduced.

The smokable products according to the invention may be used alone or ascomponents of blends of cigarette tobacco, cigar tobacco and pipetobacco. They are also suitable for use as cigar wrappers or binders oras cigarette paper.

The invention will be further described with reference to the followingexamples wherein all parts are by weight unless otherwise expressed.

EXAMPLES The smokable products produced according to the Examples weremade up into filter cigarettes with cellulose acetate filters. Thefilter cigarettes had a length of 82 mm, a diameter of 8 mm and a'buttlength of 15 mm. They were smoked down to average butt length of 23 mm.

The density of packing of the cigarettes was measured in terms of thedraft resistance. The draft resistance was determined for individualcigarettes by using a draft resistance measuring instrument supplied byFiltrona, London, which indicated the pressuredrop in mm H O. i

The filter cigarettes produced from the smokable products generally haddraft resistances of from to mm H O.

The quantities of condensate given in the examples were quantities ofdry condensate in mg/cig.. They were determined in accordance withCoresta Standard No. 10. The test cigarettes were smoked with a puffvolume of 35 ml a puff time of 2 seconds and a puff frequence of 60seconds. The condensate formed was deposited on a Cambridge filter andweighed. The water content was determined by titration using theKarl-Fischer method and was subtracted from the total condensate.

The smokable products obtained in the examples were assessed for theirorganoleptic properties which were graded as follows:

a. Sharpness:

(++) usual sharpness of cellulose light sharpness, especiallywhenlighting up the cigarette hardly any sharpness, similar to that oftobacco material completely free from sharpness b. Smoking flavor:

(-ll-) usual pronounced taste of cellulose, burning paper, stronglyastringent light taste of cellulose, not astringent no taste ofcellulose, slight impairment of flavor mild, no impairment of flavor.

Example 1a 100 g of a paper-like foil of bleached sulfate cellulosehaving a surface weight of 58 g/m a thickness of 60 p. and an ashcontent of 0.06% were sprayed with a 25% aqueous solution ofmagnesium-aluminum citrate, Mg [Al (citrate) and dried so that theresulting dry foil contained 20% by weight of the chelate. The foil wascut up into strips of various lengths about 0.9 mm in width (finecigarette cut), and made up into cigarettes with an average draftresistance of l 13 mm H O using ordinary commercial cigarette papertubes with cellulose acetate filters.

When smoked, the cigarettes glowed uniformly without ignition of thesmoking product,, and the ash was gray white and self-supporting.

Organoleptic assessment:

Sharpness Smoking flavor:

Condensate; 7.3 mg

: with a surface weight of 25 g/m, a thickness of 32 p.

and an ash content of 0.08% were sprayed with a 25% aqueous solution ofmagnesium-aluminum citrate Mg [Al (citrate) and dried so that theresulting dry foil contained 20% by weight of the chelate. The treatedfoil was cut up into strips of various lengths about 0.9 mm in width(fine cigarette cut) and made up into cigarettes with an average draftresistance of 102 mm H O using ordinary commercial cigarette paper tubeswith cellulose acetate filters.

When smoked, the cigarettes glowed uniformly without ignition of thesmoking product. The ash was selfsupporting.

Organoleptic assessment:

Sharpness Smoking flavor Condensate: 5.0 mg.

Example lc 100 g of a paper-like foil produced in known manner on aFourdrinier machine from about 60% by weight of ground tobacco ribs, 30%by weight of tobacco leaf waste (fragments and dust) and 10% by weightof unground sulfate cellulose and having a surface weight of 70 g/m anda thickness of 60 11,, were sprayed with a 25% solution ofmagnesium-aluminum citrate, Mg [Al (citrate) and dried so that theimpregnated foil contained 5% by weight of the chelate. The resultingproduct was cut up and made into filter cigarettes as in Example 1a. Thecigarettes had an average draft resistance of 109 mm H O.

The cigarettes glowed uniformly. The main stream smoke and subsidiarystream smoke were assessed as being distinctly aromatic.

Organoleptic assessment:

Sharpness: Smoking flavor Condensate: 6.2 mg

Example 2 A product was produced as described in Example la but with theaddition of magnesium citrate instead of magnesium-aluminium citrate.This was obtained as follows:

100 g of a paper-like foil as described in Example In consisting ofbleached sulfate cellulose, having a surface weight of 58 g/m and athickness of 60 p, and containing 1 1.3% by weight of magnesiumcarbonate as a filler, were immersed in a aqueous citric acid solutionat 30C. so that the product contained magnesium citrate produced insitu. When the excess citric acid had been washed out and the foildried, the weight increase of the foil was found to be 19 g, whichcorresponds to a magnesium citrate content of 22% by weight. Theresulting product was cut up and made into filter cigarettes as inExample la. The cigarettes had an average draft resistance of 102 mm HO. Organoleptic assessment:

Sharpness: (4+) Condensate: 9.3 mg/Cig.

Example 3a 100 g of a paper-like foil according to Example lb weresprayed with a 25% aqueous solution of magnesium-iron-(lII)-citrate, Mg[Fe(citrate) and dried so that the dried foil contained by weight ofchelate. The resulting product was cut up into strips of various lengthsabout 0.9 mm in width and made up into cigarettes with a draftresistance of 115 mm H O by the method described in Example la.

When smoked, the cigarettes glowed like tobacco without ignition of thesmoking product. The ash was brownish gray and self-supporting.

Organoleptic assessment:

Sharpness: Smoking flavor Condensate: 4.5 mg

EXAMPLE 3b 300 g of dried, cut stalks of shield fern (Dryopterisfilix-mas) were heated to 105C. with 6 litres of a Spercent aluminumsulfate solution for 4 hours in a 10 1 pressure vessel. The decomposedplant material was then filtered and washed free from sulphate withwater. It was then pulped up in a Hollander and made up into a web witha surface weight of 68 glm and a.thickness of 60 on a Fourdriniermachine. g of the resulting foil were sprayed with a l0percentmagnesium-iron citrate solution and dried so that the foil containedl0percent by weight of chelate. The resulting product was then cut upand made into filter cigarettes as in Example la. The cigarettes had anaverage draft resistance of 120 mm H O. They were mild in the mainstream smoke and had a pleasant, plant-like flavor. Organolepticassessment:

Sharpness:

Smoking flavor Condensate: 5.2 mg/Cig EXAMPLE 3c g of a paper-like foilproduced in known manner on a Fourdrinier machine from about 60percentby weight of ground tobacco ribs, 30percent by weight of tobacco waste(fragments and dust) and l0percent by weight of unground sulfatecellulose, and having a surface weight of 70 glm and a thickness of 60u, were sprayed with a 5% aqueous solution ofmagnesiumiron-(Ill)-citrate, Mg [Fe(citrate) and dried so that theweight increase after drying was Spercent, i.e. the chelate content wasSpercent by weight. The cigarettes produced in accordance with Examplela, which had a draft resistance of 1 15 mm H O, glowed uniformly. Theash was brownish red and self-supporting.

When smoked, the product had a light, aromatic flavor without cellulosicsharpness.

Organoleptic assessment:

Sharpness: Smoking flavor:

Condensate: 4.4 mg/Cig.

Example 4 A paper-like foil similar to that described in Example lb wasrepeatedly dipped alternately into a saturated calcium hydroxidesolution and then into a l0percent tartaric acid solution and thenwashed and dried until the weight increase was 25.3percent by weight,i.e. the foil contained about 20percent by weight of calcium tartrate.The product produced in this way was cut up as in Example 1 (finecigarette cut), and made up into filter cigarettes with a draftresistance of l 17 mm H O.

The cigarettes had a dull, musty after-taste and very pronouncedcellulosic sharpness.

Organoleptic assessment:

Sharpness: Smoking flavor: (-ll-) Condensate: 8.4 mg/Cig.

EXAMPLE A paper-like foil according to Example la was treated in anaqueous immersion bath containing 12.6percent by weight ofmagnesium-aluminum tartrate Mg [Al(tartrate) squeezed off between steelrollers and dried so that the impregnated web showed a weight increaseof 24.8percent, which corresponded to a chelate content of percent byweight. The resulting product was cut up as in Example la and made upinto filter cigarettes which had an average draft resistance of 115 mm HO. The cigarettes glowed slowly and constantly and formed a pale,self-supporting ash. Organoleptic assessment:

Sharpness:

Smoking flavor:

Condensate: 6.8 mg/Cig.

Example 6 100 g of a paper-like foil according to Example 1a weresprayed with a percent manganese-iron-(lll) oxalate solution, Mn[Fe(oxalate) and dried so that the treated foil contained 20percent byweight of the chelate. The resulting product was cut up and made up intofilter cigarettes in a manner analogous to Example la. Draft resistance:123 mm H O. The cigarettes glowed very uniformly and formed a brown,self-supporting ash.

Organoleptic assessment:

Sharpness: Smoking flavor:

Condensate: 4.2 mg/Cig.

EXAMPLE 7 100 g of a paper-like foil according to Example la weresprayed several times with a total of 250 ml of a IOpercentmagnesium-aluminum glycolate solution, Mg [Al(glycolate) and dried sothat the chelate content was 20percent by weight.

The resulting product was made up into filter cigarettes as in Example1a. The cigarettes had a draft resistance of 122 mm H O. They gloweduniformly and formed a light white ash.

Organoleptic assessment:

Sharpness: Smoking flavor:

Condensate: 7.0 mg/Cig.

EXAMPLE 8 100 g of a paper-like foil according to Example lbwere sprayedwith a l2percent solution of manganese-iron galactarate, Mn[Fe(galactarate) and dried. The foil contained 19.5percent by weight ofthe chelate.

The material cut up as in Example la and made up into filter cigaretteshaving a draft resistance of 121 mm H O glowed uniformly and formed abrownish gray ash.

Organoleptic assessment:

Sharpness: Smoking flavor:

Condensate: 4.9 mg/Cig.

EXAMPLE 9 A mixture of percent weight of the impregnated foil fromExample la, and 70percent by weight of an American Virginia tobaccohaving a condensate of 28 mg/Cig. was made up into filter cigaretteswith a draft resistance of 126 mm H O. The aromatic substances and thecharacteristic sweetness of Virginia tobacco were found to be completelypreserved when the mixture was smoked. The nicotine reaction on therespiratory tract was considerably attenuated; Organoleptic assessment:

Sharpness:

Smoking flavor: Condensate: l5 mg/Cig.

EXAMPLE 10 A mixture of 30percent by weight of the foil from Example3aand percent by weight of an Italian Burley tobacco having a condensateof 22 mg/Cig. was made up into filter cigarettes with an average draftresistance of 121 mm H O. The cigarettes were found when smoked to havethe complete characteristic cigar-like flavour of Burley tobacco.Organoleptic assessment:

Sharpness:

Smoking flavor:

Condensate: l2 mg/Cig.

EXAMPLE 1 l A mixture of 30percent by weight of the foil from Example 6and 70percent by weight of a commercial tobacco mixture with a lightnote (American blend type flavor having a condensate of 15 mg/Cig. wasmade up into filter cigarettes. The cigarettes were found when smoked tohave a pleasant, mild flavor. The smoke appeared much thinner than thatproduced by the tobacco mixture alone. The glowing process was similarto that of natural tobacco in its uniformity and rate. Draft resistance:1 18 mm H O Organoleptic assessment:

Sharpness:

Smoking flavor:

Condensate: 9.3 mg Cig.

EXAMPLE 12 The combustible material used as a tobacco which wascharacterized as rough Burley with a strong cigar note. This tobacco wassprayed with a solution of ammonium-iron (lll) citrate, (Nl-l[Fe(citrate) and acid magnesium-aluminum tartarate, Mg H [Al (tart) in aratio by weight of 1:1, so that the amount of dry substance taken up was2.5percent by weight, i.e. the amount of each compound present in thetreated tobacco material is 1.25percent by weight.

Compared with this material, the Burley tobacco which has been treatedby the process according to the invention was less sharp when smoked butwith an overall spicy aromatic flavor. The Burley note was completelypreserved.

Assessment:

Sharpness:

Smoking flavor:

Example 13 The combusticle material used was a paper-like foil producedfrom a 1:1 mixture of ground tobacco ribs and sulfate cellulose andhaving a surface weight of 45 g/mand a thickness of 55 This material wastreated in an immersion bath containing 15 parts by weight ofmagnesium-aluminum citrate, Mg [Al (citrate) 6 parts of ammoniumaluminum citrate, (NH [Al (citrate) 4 parts of aluminum hydroxide, 4parts of silicic acid, 1 1 parts of tobacco extract and 60 parts ofwater. The treated foil was squeezed off and dried in a stream of air at95C. A weight increase of 55% by weight was obtained. The componentsdissolved in the immersion bath were incorporated in the foil at thesame concentration ratio, i.e. the foil contained 13.6% by weight of Mg[Al (citrate) and by weight of (NI-l [Al (citrate) Compared with aproduct obtained without the addition of chelate, the smokable productobtained had no astringent effect, was free from sharpness and produceda light, aromatic smell. It was found to be completely compatible withcommercial cigarette tobaccos with which it was blended.

Assessment:

Sharpness: Smoking flavor:

Examples 14-22 Chelate complexes on Cellulose webs Paper-like foils orwebs with and without fillers were produced on a paper-machine to beused as starting Foils A to D were prepared in an immersion bathconsisting of the aqueous solution of the chelate together with thecompound which splits off ammonia when smoked. In Examples l5, l7, l8and l9, the immersion bath contains in addition a filler and a binder.The immersed foil was squeezed off in its passage through rollers anddried on an endless band in an air stream at 95C.

Table III summarizes for Examples 14 to 22 the nature of the foil usedas combustible material, the composition of the immersion bath, theincrease in dry weight of the treated foil.(total weight increase andincrease due to chelate content) and the assessment of the organolepticproperties of the resulting smokable products as well as the condensatevalues. The quantity of solids taken up by the foil (compounds whichsplit off ammonia, fillers) is obtained from the weight increase, theindividual constituents being taken up into the foil in the same ratioby weight as that found in the immersion bath. The quantity of chelatestaken up is indicated separately.

Table 111 EX. Composition of the immersion bath Solids Assessment takenup* (Foil) Chelate Compound which Filler Binder Total Chelate Sharp-Cellulose Condensate (g/l) splits off (g/l) (g/l) ness flavor ammonia(g/l) 14 200 g of magnesl00 g of 29.6 20.0 9.7 (A) ium-aluminum ammoniumcitrate tartrate Mg=[Al (citrate) 15 100 g of magnes- 100 g of 250 g 10g 5.7 8.3 (A) ium-aluminum ammonium Al(OH) of gum citrate tartratearabic Mg [Al(citrate) lo 200 g of magnes- 50 g of 36 4 29.1 9 6 (A)ium-aluminum urea citrate Mg [Al(citrate,] l7 l90 g of acid g of urea200 g 30 g 56 20.0 6.3 (B) magnesium-alum- 84 g of ammoniumof of inumtartrate aluminum Al(OH) corn M gH [Al( tartartrate starch trate) NH[Al(tartrate)] 18 100 g of magnesium 50 got urea 200 g l0 g 60 l5 4.8(B) iron (Ill) citrate 50 g of magnesium Al(OH) gum Mg [Fe(citrate)glutamate arabic I9 100 g of magnesium 200 g of ammon- 24 8 l 8 5 (C)aluminum citrate ium citrate Mg [Al(citrate) 20 I00 g of magnesium 200 gof ammonium 250 g 8 g 7.3 7.8 (C) aluminum citrate citrate Al(OH of gumMg [Al(citrate),] arabic 2l l20 g of magnesium g of urea l9 5 l3 1 5 5(C) iron-(ill) citrate 10 g of magnes- Mg [Fe(citrate) ium glutamate 22g of magnesium g of l6 6 0 7 3 (D) aluminum citrate ammonium Mg -,[Al(citrate) tartrate Increase in by weight after drying, based on theoriginal foil.

materials for the smoking products. A description of the foils obtainedis summarized in Table II.

Examples 23-25 Tobacco mixtures The cut foils from Examples 15, 16 and18 were mixed with a commercial cigarette tobacco with'a light note andmade up into filter cigarettes.

Example 23 A 30% mixture of the foil from Example 15 and a commercialcigarette tobacco with a light note resalted in a round, soft aromawithout any cellulosic sharpness. The only effect of the low nicotinecontent in the total mixture was an attenuation of the reaction toinhalation of the main stream smoke. Assessment:

Sharpness: Smoking flavor: Condensate: 13.6 mg

Example 24 A 30% mixture of the foil from Example 16 resulted in aslightly attenuated aromatic impression in the tobacco mixture with alow residual sharpness The nicotine reaction on inhalation of the mainstream smoke was the same as in Example 13.

Assessment:

Sharpness: Smoking flavor:

Condensate: 14.1 mg

Example 25 Examples 2631 Foils from Examples 14-22 were immersed inaccordance with the following Examples 26-31 in a solution of aqueoustobacco extract containing about 30% by weight of soluble tobaccoconstituents or sprayed with this solution so that the dry weightincrease was up to 50% by weight. Drying was carried out using hot airat 60C. to 100C.

Example 26 of the constituents of commercial tobacco mixture with anAmerican Blend type flavor were extracted using a cold methanol/watersolution (70 vol/30 vol). This aqueous-methanolic extract was sprayed onthe smoking product produced according to Example 17 so that the dryweight increase was 30% by weight. The resulting product was made upinto filter cigarettes which gave an aromatic overall impression withoutsharpness in the main stream (assessment and no cellulosic after-taste(assessment: on inhalation, with a distinctly perceptible nicotinereaction and a fully aromatic side stream. The resulting smokableproduct was compatible when mixed in any proportion with Virginia,Burley and Orient type tobaccos and mixtures of such tobaccos(Condensate: 9.8 mg).

Example 27 The foil obtained according to Example 19 was treated withthe same extract of tobacco constituents as in Example 26 to result in adry weight increase of 29% by weight. The flavor of the product made upinto filter cigarettes was assessed as inert with little aroma and withonly a slight sharpness (assessment: when the cigarette was lit up. Theside stream smoke was aromatic and mild (assessment of smoking flavor:condensate: 10.7 mg).

Example 28 The foil obtained according to Example 20 was treated withthe same extract of tobacco constituents as in Example 26 so that theincrease in dry. weight was about 25% by weight. Compared with Example27, a fuller flavor was obtained with a good reaction, and even whenlighting up the cigarette no sharpness (assessment: and no cellulosicafter-taste (assessment: were experienced. The side stream smoke waspleasantly aromatic. (Condensate: 9.0 mg).

Example 29 The constituents of American Virginia tobacco were completelyextracted with hot water. The aqueous extract was sprayed onto thesmokable product produced according to Example 20 so that the increasein dry weight was 31%. When this cigarette was smoked, it was found tohave an unmistakable, typical Virginia flavor the spiciness of which wasnot impaired by the foil. Assessment:

Sharpness:

Smoking flavor: Condensate: 11.0 mg

Example 30 The soluble constituents were completely extracted fromItalian' Burley tobacco by means of a cold methanol/water solution (60vol/40 vol). The extract was sprayed onto the smokable product obtainedaccording to Example 22 so that the weight increase was 20%. The flavorwas that of a good quality, characteristic Burley tobacco with asweetish note. The smokable product was less sharp than the Burleytobacco used for extraction. The smokable product obtained wascompatible in any proportions with Virginia, Burley and Orient typetobaccos and mixtures thereof. Assessment:

Sharpness:

Smoking flavor:

Condensate: 11.3 mg

Example 31 Foil C indicated in Table 11 was treated in an immersion bathwhich contained 160 g of ammonium citrate, g of magnesium-aluminumcitrate, Mg [Al (citrate) and 280 g of the tobacco constituents obtainedby extraction with water in accordance with Example 19 and which hadbeen adjusted to pH 7 with ammonia. The increase in dry weight of thefoil was 50% and the resulting smokable product contained 5.1% by weightof chelate. When smoked, the product was light, aromatic and practicallyfree from any after-taste or sharpness. It was compatible with all theusual sorts of tobacco in any proportions.

Assessment:

Sharpness: Smoking flavor:

Condensate: 9.9 mg

Example 32 15 parts of ground, pure linters (99.8% a-cellulose), 15parts of aluminum hydroxide, 5 parts of magnesiumaluminum citrate, Mg[Al (citrate) and 5 parts of magnesium-iron citrate, Mg [Fe(citrate)were added to a 5% aqueous casting solution of sodium car- 20boxymethylcellulose/ammonium carboxymethylcellu- Table V shows examplesof the preparation of smoklose (3:1 able products by the processaccording to the invention The solution was cast onto apolytetrafluorethyleneand quantities of condensate formed by theseproducts. coated band using a pressure casting tool and dried at TableVI shows the production of smokable products 130C. The cast foil weighed15 g/m. A 30% by weight 5 according to Table V which in addition containpotasmixture of this product with a Virginia-Burley mixture siumpermanganate as an oxidizing agent and the quan- (proportion by weight:3:1) had a slightly weaker tities of condensate formed by theseproducts.

aroma than the Virginia Burley mixture without the Table IV product butthere was no adulteration of the aroma and no sharpness (Cond nsat 12 4Foil Cellulose Fillers Surface Thickness material weigl it p. Example 33g/m A bleached 43.5% by'weight 42 55 A commercial cigarette paper wassprayed with a 6% lf t A] (OH)3 by weight solution of 2 parts ofmagnesium-aluminum cellulose 102% by Weight citrate, Mg [Al citrate) and1 part of ammonium- B do. 44.6% by weight 50 62 aluminum citrate, (Nl-1[Al (citrate ]and dried at A] on 1 90C. The amount of salt taken up was9% by weight. c o, 40.2% by weight 54 70 Cigarettes produced using thispaper were improved in m ht flavor and aroma compared with cigarettesproduced with untreated paper because the treated paper was D d 31.1% byweight 38 45 free from sharpness and had no unpleasant cellulosic hafter-taste. t

2 E do. 16.1% by weight 32 40 Examples 34-49 Al (0): The combustiblematerials used were paper webs of F 7 3 might 25 35 bleached sulfatecellulose with different filler contents 3 and surface weights. Thecompositions of the foils used Table V Example Foil from Composition ofimmersion bath (g/l) Solids taken Condensate Table in p Total/Chelate 34A 80 Magnesium-iron citrate Mg [Fe(citrate) 20.2 10.6 3.8

a'mminium-iron citrate (NH,)=[Fe(citrate) 20 urea 20 ammonium citrate Bas in Example 34 16.8 8.9 3.7 36 C as in Example 34 17.4 9.3 4.1 37 D asin Example 34 26.6 14.0 4.3 38 'E 120 Magnesium-iron citrate Mg[Fe(citrate) 27.5 18.7 6.6

50 urea 10 magnesium glutamate 39 F 160 Magnesium-iron citrate Mg[Fe(citrate) 44.0 23.0 4.8

30 ammonium-iron citrate (NH ),,[Fe(citrate)-,]' 20 urea 20 ammoniumcitrate 75 water-soluble tobacco constituents" "lncrease in by weightafter drying, based on the foil used as starting material "Obtained bycomplete extraction of Burley tobacco with hot water as combustiblestarting material are shown in Table IV.

Table VI Example Production Application of potassium permanganatePotassium Condensate of the foil permanganate as in Example content offoil by weight) 40 34 Addition of 10 g/l into the immersion bath 2.8 1.241 35 after drying, the foil treated with complex 3.0 1.9

salts is passed through an aqueous-acetonie bath of KMnO 42 36 afterdrying of the complex salt solution. 2.6 1.8

the foil is passed through an aqueous KMnO. bath 43 36 sprayed fromsolution in acetone 3.0 1.7 44 37 foil was treated with aqueous KMnOsolution 3.0 3.0

before application of the complex salts and dried 45 38 beforeapplication of the complex salts. the 2.9 2.7

foil was treated with aqueous KMnO, solution and dried 46 39 as inExample 44 2.1 2.6

Table Vl-continued Example Production Application of potassiumpermanganate Potassium Condensate of the foil permanganate as in Examplecontent of foil by weight) 46a 39 as in Example 45 2.1 2.6

Example 47a A 1% solution of citrus pectin in the form of the ammoniumsalt was sprayed onto the product produced according to Example 34 sothat the dry weight of citrus pectin taken up by the product was 1.3% byweight.

and 46 and a commercial tobacco mixture which had a nicotine content of0.86 mg and a condensate of 14.8 mg/filter cigarette. Table VII showsthe expected and found condensate contents and nicotine contents forvarious mixtures. When calculating the expected values, the bulk volumesof the various mixtures were taken into consideration.

Table VII Smokable product Tobacco Calculated condensate CondensateNicotine Nicotine from Example 29 by content (tobacco content foundcalculated found by weight) weight) smokable product (mg/Cig.) (mg/Cig)content) 80 10.7 1.3 12.0 9.9 0.62 0.45 40 60 6.7 2. 8.8 7.4 0.39 0.2860 40 3.5 2.4 5.9 4.4 0.22 0.17 Smokable product from Example 36 byweight) v The material made u into ci arettcs and smoked p g EXAMPLE 51was found when compared with the product according to Example 34 to havean improved, pleasantly fresh and slightly plant-like flavor and thesame condensate value.

Example 47b A mixture of by weight of the product according to Example47a and 70% by weight of a commercial fine cut tobacco mixture with thetype of flavor of an American blend was made up into cigarettes. Theflavor produced by the pectin in the main stream smoke was completelycompatible with the tobacco aroma and rounded off the aroma bouquet.

Example 48 A 2% solution of zein in ethanol was sprayed onto the productproduced according to Example so that the weight increase due to thezein was 1.7% after drying.

The product made up into cigarettes was found when smoked to produce animproved aroma in the main stream and subsidiary stream smoke comparedwith the product according to Example 35 and had the same condensatevalue.

Example 49 A 2% ethanolic solution of zein was sprayed onto the productmade according to Example 39 so that the weight increase due to the zeinwas 1.5% by weight after drying.

The product made up into cigarettes had a much Example 50 Mixtures wereprepared as indicated in Table V11 from the smoking products accordingto Example 39 The foil produced according to Example 36 was sprayed withan aqueous alcoholic solution of potassium nitrate and dried, theincrease in dry weight being 1%. Condensate: 3.1 mg/Cig.

Example 52 The foil produced according to Example 36 was sprayed with anaqueous potassium nitrate solution and dried, the increase in dry weightbeing 2%. Condensate: 2.5 mg/Cig.

Example 53 A foil produced according to Example 38 was sprayed with anaqueous potassium nitrate solution and dried, the increase in dry weightbeing 2%. Condensate: 3.2 mg/Cig.

Example 54 A combustible material in the form of a paper web of bleachedsulfate cellulose containing 45% by weight of aluminum hydroxide as afiller and having a surface weight of 50 g/m and a thickness of 38 p.was treated in an immersion bath containing:

10 parts of manganese-iron citrate, Mn [Fe(citrate) 6 parts ofammonium-iron citrate, (Nl-l [Fe(citrate) 5 parts of urea 12 parts oftobacco constituents obtained buy complete extraction of Burley tobaccowith hot water 100 parts of water, so that, after drying at temperaturesconstantly increasing from 55C to C, the increase in dry weight was 34%.The resulting smokable product contained 7.6% by weight of the chelate.It was made up into filter cigarettes. The product was assessedorganoleptically as neutral in flavor with a marked impression oftobacco. Condensate: 3.1 mg/Cig.

Example 55 A combustible material as in Example 54 consisting of a foilof bleached sulfate cellulose which contained 45% by weight of aluminumhydroxide as a filler and which had been pretreated with a 2% aqueouspotassium permanganate solution was treated in an immersion bath whichconsisted of:

8 parts of manganese-iron galactarate, Mn [Fe(- galactarate) 8 parts ofmagnesium-aluminum citrate, Mg [Al (citrate 6 parts of ammonium irongalactarate, NI-I [Fe(- galactarate)] 6 parts of urea 12 parts oftobacco constituents (which had been obtained according to Example 29)100 parts of water so that, after drying at 55C. to 95C with constantlyincreasing temperature, the increase in dry weight was 41%. Theresulting smokable product contained 1 1.4% by weight of the chelate. Itwas made up into filter cigarettes. The product was assessedorganoleptically as exceptionally mild and tobacco-like. Condensate: 2.8mg/Cig.

The product obtained by this Example was exceptionally compatible with acommercial tobacco mixture which had a light note.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. In a smokable product comprising a cellulosebased combustiblematerial, the improvement which comprises incorporating therein at leastone chelate compound of the stoichiometric formula.

K is an alkaline earth metal or divalent manganese,

Me is trivalent iron or aluminum,

R is the radical of a chelate-forming organic carboxylic acid, and

w, x, y and z are integers up to about 5, the chelate compound beingincorporated in an amount ranging from about 0.5 to 70% by weight of thecombustible material.

2. A smokable product according to claim 1, wherein K is magnesium.

3. A smokable product according to claim 1, wherein the organiccarboxylic acid has from 2 to 8 carbon atoms and is substituted with atleast one hydroxy or keto group or has at least two carboxylic acidgroups.

4. A smokable product according to claim 3, wherein the organiccarboxylic acid is a material selected from the group consisting ofoxalic, glyceric, glycolic, malic, tartaric, citric, galactaric andsaccharic acids.

5. A smokable product according to claim 1, whereinxis1or2andyisfrom1to4.

6. A smokable product according to claim 1, wherein the chelate compoundis incorporated in an amount ranging from about to 50% by weight of thecombustible material.

7. A smokable product according to claim 1, wherein the chelate compoundis a material selected from the group consisting of magnesium-iron (III)glycolate, magnesium-iron (III)-oxalate, magnesium-iron (III) citrate,magnesium-iron (III) tartrate, magnesium-iron (III) galactarate,magnesium-iron (III) saccharate, magnesium-aluminum glycolate,magnesium-aluminum oxalate, magnesium-aluminum citrate,magnesiumaluminum tartrate, magnesium-aluminum galactarate,magnesium-aluminum-saccharate, manganese-iron (III) glycolate,manganese-iron (III) oxalate, manganese-iron (III) citrate,manganese-iron (III) tartrate, manganese-iron (III) galactarate,manganese-iron (III) saccharate, manganese-aluminum glycolate,manganese-aluminum oxalate, manganese-aluminum citrate,manganese-aluminum tartrate, manganesealuminum galactarate andmanganese-aluminum saccharate.

8. A smokable product according to claim 1, containing about 1 to byweight of at least one filler selected from the group consisting ofminerals and salts which are inert under conditions of smoking, andhydroxides and hydrated oxides which split off water under conditions ofsmoking.

9. A smokable product according to claim 8, wherein the filler is atleast one material selected from the group consisting of hydrated oxidesof aluminum and silicic acid.

10. A smokable product according to claim 1, containing at least onecompound which splits off ammonia under conditions of smoking and whichis present in an amount such that the smoke has a pH of about 5 to 8.

11. A smokable product according to claim 10, wherein the compound whichsplits off ammonia is at least one material selected from the groupconsisting of ammonium salts of inorganic acids, ammonium salts oforganic acids, salts of amino acids and acid amides.

12. A smokable product according to claim 10, wherein the compound whichsplits off ammonia is at least one material selected from the groupconsisting of acid or neutral ammonium carbonate, nitrate or phosphate,ammonium citrate, ammonium tartrate, ammonium or magnesium glutamate,urea, ammonium-iron (III) glycolate, ammonium-iron (III) oxalate,ammonium-iron (III) citrate, ammonium-iron (III) tartrate,ammonium-iron-(III) galactarate, ammonium-iron (III) saccharate,ammonium-aluminum glycolate, ammonium-aluminum oxalate,ammonium-aluminum citrate, ammonium-aluminum tartrate, ammonium-aluminumgalactarate and ammonium-aluminum saccharate.

13. A smokable product according to claim 1, containing about 0.01 to 7%by weight of at least one oxidizing agent selected from the groupconsisting of alkali metal or alkaline earth metal nitrates and alkalimetal permanganates.

14. A smokable product according to claim 1, containing about 0.01 to10% by weight of the ammonium salt of at least one polymeric acidselected from the group consisting of pectin, alginic acid, gum arabicor carboxymethylcellulose.

15. A smokable product according to claim 1, containing about 0.01 to 5%by weight of at least one low sulfur-content protein selected from thegroup consisting of zein, hordein and gliadin.

16. A smokable product according to claim 1, containing about 0.1 to 50%by weight of a tobacco extract.

17. A smokable product according to claim 7, wherein x is 1 or 2 and yis from 1 to 4 and the chelate compound is incorporated in an amountranging from about 5 to 50% by weight of the product; said productoptionally containing about 1 to 70% by weight of at least one materialselected from the group consisting of hydrated oxides of aluminum andsilicic acid; at least one compound which splits off ammonia underconditions of smoking and which is present in an amount such that thesmoke has a pH of about 5 to 8, said compound being selected from thegroup consisting of acid or neutral ammonium carbonate, nitrate andphosphate, ammonium citrate, ammonium tartrate, ammonium or magnesiumglutamate, urea, ammonium-iron (III) glycolate, ammonium-iron (III)oxalate, ammonium-iron (III) citrate, ammonium-iron (III) tartrate,ammonium-iron-(III) galactarate, ammonium-iron (III) saccharate,ammonium-aluminum glycolate, ammonium-aluminum oxalate,ammonium-aluminum citrate, ammonium-aluminum tartrate, ammonium-aluminumgalactarate and ammonium-aluminum saccharate, about 1 to 5% by weight ofat least one oxidizing agent selected from the group consisting ofalkali metal or alkaline earth metal nitrates and alkali metalpermanganates; about 0.01 to by weight of the ammonium salt of at leastone polymeric acid selected from the group consisting of pectin, alginicacid, gum arabic or carboxymethylcellulose; about 0.01 to 5% by weightof at least one low sulfur-content protein selected from the groupconsisting of zein, hordein and gliadin; and about 0.1 to 50% by weightof a tobacco extract; said cellulose-based combustible material being inthe form of a paper-like web of about 10 to 120 p. in thickness andweighing about 10 to 250 grams per square meter.

18. A smokable product according to claim 17, blended with tobacco.

19. A smokable product according to claim 1, in the form of a cigaretteor cigar.

20. The process for making a smoking product according to claim 17 whichcomprises applying to a paper-like web of said cellulose-basedcombustible material of about 10 to p. in thickness an aqueous solutioncontaining said chelate compound, said filler, said compound whichsplits off ammonia, said oxidizing agent, said ammonium salt ofpolymeric acid, said protein and said tobacco extract, and drying,application being effected by spraying or painting said solution ontosaid web or by immersing said web in said solution, the impregnated webon a solvent-free basis weighing about 10 to 250 grams per square meter.

21. The process for making a smoking product according to claim 17,which comprises forming a solution containing said cellulose-basedcombustible material, said chelate compound, said filler, said compoundwhich splits off ammonia, said oxidizing agent, said ammonium salt ofpolymeric acid, said protein and said tobacco extract, casting saidsolution to form a sheet having a solvent-free weight of about 10 to 250grams per square meter, and drying said sheet to remove the solvent andleave the sheet with a thickness of about 10 to 120 p" 22. A smokableproduct according to claim 1, wherein the' combustible material isselected from the group consisting of tobacco, tobacco waste products,hay, straw, lupins, fern, cellulose, wood pulp, carboxymethyl cellulose,hydroxyethyl cellulose and methyl cellulose.

1. IN A SMOKABLE PRODUCT COMPRISING A CELLULOSE-BASED COMBUSTIBLEMATERIAL, THE IMPROVEMENT WHICH COMPRISES INCORPORATING THEREIN AT LEASTONE CHELATE COMPOUND OF THE STOICHIOMETRIC FORMULA.
 2. A smokabLeproduct according to claim 1, wherein K is magnesium.
 3. A smokableproduct according to claim 1, wherein the organic carboxylic acid hasfrom 2 to 8 carbon atoms and is substituted with at least one hydroxy orketo group or has at least two carboxylic acid groups.
 4. A smokableproduct according to claim 3, wherein the organic carboxylic acid is amaterial selected from the group consisting of oxalic, glyceric,glycolic, malic, tartaric, citric, galactaric and saccharic acids.
 5. Asmokable product according to claim 1, wherein x is 1 or 2 and y is from1 to
 4. 6. A smokable product according to claim 1, wherein the chelatecompound is incorporated in an amount ranging from about 5 to 50% byweight of the combustible material.
 7. A smokable product according toclaim 1, wherein the chelate compound is a material selected from thegroup consisting of magnesium-iron (III) glycolate, magnesium-iron(III)-oxalate, magnesium-iron (III) citrate, magnesium-iron (III)tartrate, magnesium-iron (III) galactarate, magnesium-iron (III)saccharate, magnesium-aluminum glycolate, magnesium-aluminum oxalate,magnesium-aluminum citrate, magnesium-aluminum tartrate,magnesium-aluminum galactarate, magnesium-aluminum-saccharate,manganese-iron (III) glycolate, manganese-iron (III) oxalate,manganese-iron (III) citrate, manganese-iron (III) tartrate,manganese-iron (III) galactarate, manganese-iron (III) saccharate,manganese-aluminum glycolate, manganese-aluminum oxalate,manganese-aluminum citrate, manganese-aluminum tartrate,manganese-aluminum galactarate and manganese-aluminum saccharate.
 8. Asmokable product according to claim 1, containing about 1 to 70% byweight of at least one filler selected from the group consisting ofminerals and salts which are inert under conditions of smoking, andhydroxides and hydrated oxides which split off water under conditions ofsmoking.
 9. A smokable product according to claim 8, wherein the filleris at least one material selected from the group consisting of hydratedoxides of aluminum and silicic acid.
 10. A smokable product according toclaim 1, containing at least one compound which splits off ammonia underconditions of smoking and which is present in an amount such that thesmoke has a pH of about 5 to
 8. 11. A smokable product according toclaim 10, wherein the compound which splits off ammonia is at least onematerial selected from the group consisting of ammonium salts ofinorganic acids, ammonium salts of organic acids, salts of amino acidsand acid amides.
 12. A smokable product according to claim 10, whereinthe compound which splits off ammonia is at least one material selectedfrom the group consisting of acid or neutral ammonium carbonate, nitrateor phosphate, ammonium citrate, ammonium tartrate, ammonium or magnesiumglutamate, urea, ammonium-iron (III) glycolate, ammonium-iron (III)oxalate, ammonium-iron (III) citrate, ammonium-iron (III) tartrate,ammonium-iron-(III) galactarate, ammonium-iron (III) saccharate,ammonium-aluminum glycolate, ammonium-aluminum oxalate,ammonium-aluminum citrate, ammonium-aluminum tartrate, ammonium-aluminumgalactarate and ammonium-aluminum saccharate.
 13. A smokable productaccording to claim 1, containing about 0.01 to 7% by weight of at leastone oxidizing agent selected from the group consisting of alkali metalor alkaline earth metal nitrates and alkali metal permanganates.
 14. Asmokable product according to claim 1, containing about 0.01 to 10% byweight of the ammonium salt of at least one polymeric acid selected fromthe group consisting of pectin, alginic acid, gum arabic orcarboxymethylcellulose.
 15. A smokable product according to claim 1,containing about 0.01 to 5% by weight of at least one low sulfur-contentprotein selected from the group consisting of zein, hordein and gliadin.16. A smokabLe product according to claim 1, containing about 0.1 to 50%by weight of a tobacco extract.
 17. A smokable product according toclaim 7, wherein x is 1 or 2 and y is from 1 to 4 and the chelatecompound is incorporated in an amount ranging from about 5 to 50% byweight of the product; said product optionally containing about 1 to 70%by weight of at least one material selected from the group consisting ofhydrated oxides of aluminum and silicic acid; at least one compoundwhich splits off ammonia under conditions of smoking and which ispresent in an amount such that the smoke has a pH of about 5 to 8, saidcompound being selected from the group consisting of acid or neutralammonium carbonate, nitrate and phosphate, ammonium citrate, ammoniumtartrate, ammonium or magnesium glutamate, urea, ammonium-iron (III)glycolate, ammonium-iron (III) oxalate, ammonium-iron (III) citrate,ammonium-iron (III) tartrate, ammonium-iron-(III) galactarate,ammonium-iron (III) saccharate, ammonium-aluminum glycolate,ammonium-aluminum oxalate, ammonium-aluminum citrate, ammonium-aluminumtartrate, ammonium-aluminum galactarate and ammonium-aluminumsaccharate; about 1 to 5% by weight of at least one oxidizing agentselected from the group consisting of alkali metal or alkaline earthmetal nitrates and alkali metal permanganates; about 0.01 to 10% byweight of the ammonium salt of at least one polymeric acid selected fromthe group consisting of pectin, alginic acid, gum arabic orcarboxymethylcellulose; about 0.01 to 5% by weight of at least one lowsulfur-content protein selected from the group consisting of zein,hordein and gliadin; and about 0.1 to 50% by weight of a tobaccoextract; said cellulose-based combustible material being in the form ofa paper-like web of about 10 to 120 Mu in thickness and weighing about10 to 250 grams per square meter.
 18. A smokable product according toclaim 17, blended with tobacco.
 19. A smokable product according toclaim 1, in the form of a cigarette or cigar.
 20. The process for makinga smoking product according to claim 17 which comprises applying to apaper-like web of said cellulose-based combustible material of about 10to 120 Mu in thickness an aqueous solution containing said chelatecompound, said filler, said compound which splits off ammonia, saidoxidizing agent, said ammonium salt of polymeric acid, said protein andsaid tobacco extract, and drying, application being effected by sprayingor painting said solution onto said web or by immersing said web in saidsolution, the impregnated web on a solvent-free basis weighing about 10to 250 grams per square meter.
 21. The process for making a smokingproduct according to claim 17, which comprises forming a solutioncontaining said cellulose-based combustible material, said chelatecompound, said filler, said compound which splits off ammonia, saidoxidizing agent, said ammonium salt of polymeric acid, said protein andsaid tobacco extract, casting said solution to form a sheet having asolvent-free weight of about 10 to 250 grams per square meter, anddrying said sheet to remove the solvent and leave the sheet with athickness of about 10 to 120 Mu .
 22. A smokable product according toclaim 1, wherein the combustible material is selected from the groupconsisting of tobacco, tobacco waste products, hay, straw, lupins, fern,cellulose, wood pulp, carboxymethyl cellulose, hydroxyethyl celluloseand methyl cellulose.